Restricted rotation dynamics and far-infrared spectra of liquid water governed by elastic interactions

A semi-phenomenological model describing wideband dielectric and far-infrared spectra of liquid water was proposed recently by the same authors [J. Mol. Struct. 606 (2002) 9], where a small dipole-moment component changing harmonically with time determines a weak absorption band (termed here the R-band) centred at the wavenumber v similar to 200 cm(-1). In the present work, a rough molecular theory of the R-band based on the concept of elastic interactions is given. Stretching and bending of hydrogen bonds cause restricted rotation (RR) of a polar water molecule in terms of a dimer comprising the H- bonded molecules. Analytical expression for the RR frequency nu(str) is derived as a function of the RR amplitude, geometrical parameters and force constants. The density g(nu(str)) of frequency distribution is shown to be centred in the R-band. The spectrum of the dipolar auto-correlation function calculated for this structural-dynamical model is found. A composite model comprising two intermolecular potentials is proposed, which yields for water a good description of the experimental wideband (from 0 to 1000 cm(- 1)) spectra of complex permittivity and of absorption coefficient. The presented interpretation of these spectra is based on a concept that water presents a two-component solution, with components differing by the types of molecular rotation. (C) 2003 Elsevier B.V. All rights reserved.

Analytical calculation of far infrared spectra of ice in terms of a molecular model

Wideband far infrared (FIR) spectra of complex permittivity e(p) of ice are calculated in terms of a simple analytical theory based on the method of dipolar autocorrelation functions. The molecular model represents a revision of the model recently presented for liquid water in Adv. Chem. Phys. 127 (2003) 65. A composite two-fractional model is proposed. The model is characterised by three phenomenological potential wells corresponding to the three FIR bands observed in ice. The first fraction comprises dipoles reorienting in a rather narrow and deep hat-like well; these dipoles generate the librational band centred at the frequency approximate to 880 cm(-1). The second fraction comprises elastically interacting particles; they generate two nearby bands placed around frequency 200 cm(-1). For description of one of these bands the harmonic oscillator (HO) model is used, in which translational oscillations of two charged molecules along the H-bond are considered. The other band is produced by the H-bond stretch, which governs hindered rotation of a rigid dipole. Such a motion and its dielectric response are described in terms of a new cut parabolic (CP) model applicable for any vibration amplitude. The composite hat-HO-CP model results in a smooth epsilon(nu) ice spectrum, which does not resemble the noise-like spectra of ice met in the known literature. The proposed theory satisfactorily agrees with the experimental ice spectrum measured at - 7 degrees C. The calculated longitudinal optic-transverse optic (LO-TO) splitting occurring at approximate to 250 cm(-1) qualitatively agrees with the measured data. (c) 2004 Elsevier B.V. All rights reserved.

Specific and unspecific interactions in polar fluids in view of wideband dielectric far-infrared spectra

A simple molecular analytical theory of dielectric relaxation in strongly polar fluids is considered in terms of a semi- phenomenological approach. Theoretical spectra epsilon(v), a(v) of complex permittivity and absorption coefficient are fully determined by a form of intermolecular potential well, in which a dipole reorients. In a recent publication by VI. Gaiduk, O.F. Nielsen, and T.S. Perova [J. Molliq 95 (1002) 1-25] the wideband spectra of liquid H2O and D2O were described in terms of a composite model comprising the rectangular and the cosine squared potential wells. Much better results are achieved in this work, where the rectangular well is replaced by a well with a rounded bottom termed the hat-curved well. The spectrum of the auto-correlation function (ACF) is calculated for such a potential. The proposed theory of a composite model, comprising hat-curved and parabolic wells, is applied for liquid water. This model is capable for describing the Debye relaxation region, the second relaxation region in the submillimeter wavelength range, and the far infra-red (FIR) e(v), a(v) spectra, where an intense librational band and an additional weak band are placed, respectively, near 700 cm(-1) and 200 cm(-1). The latter band reflects the features of so-called specific (viz. directly related to H-bonds) interactions and the former band reflects the features of unspecific interactions. The physical mechanisms connected with these types of interactions are discussed in terms of two relevant types of water structure (types of molecular rotation). The proposed theory is also applied to a non-associated liquid in terms of one hat-curved potential well. (C) 2004 Elsevier B.V. All rights reserved.

Measurement and interpretation of the mid-infrared properties of single crystal and polycrystalline gold

The contribution of electron-phonon scattering and grain boundary scattering to the mid-IR (lambda = 3.392 mum) properties of An has been assessed by examining both bulk, single crystal samples-Au(1 1 1) and Au(1 1 0)-and thin film, polycrystalline An samples at 300 K and 100 K by means of surface plasmon polariton excitation. The investigation constitutes a stringent test for the in-vacuo Otto-configuration prism coupler used to perform the measurements, illustrating its strengths and limitations. Analysis of the optical response is guided by a physically based interpretation of the Drude model. Relative to the reference case of single crystal Au at 100 K (epsilon = - 568 + i17.5), raising the temperature to 300 K causes increased electron-phonon scattering that accounts for a reduction of similar to40 nm in the electron mean free path. Comparison of a polycrystalline sample to the reference case determines a mean free path due to grain boundary scattering of similar to 17 nm, corresponding to about half the mean grain size as determined from atomic force microscopy and indicating a high reflectance coefficient for the An grain boundaries. An analysis combining consideration of grain boundary scattering and the inclusion of a small percentage of voids in the polycrystalline film by means of an effective medium model indicates a value for the grain boundary reflection coefficient in the range 0.55-0.71. (C) 2005 Elsevier B.V. All rights reserved.

Single-shot characterisation of independent femtosecond extreme ultraviolet free electron andf infrared laser pulses

Two-color above threshold ionization of helium and xenon has been used to analyze the synchronization between individual pulses of the femtosecond extreme ultraviolet (XUV) free electron laser in Hamburg and an independent intense 120 fs mode-locked Ti:sapphire laser. Characteristic sidebands appear in the photoelectron spectra when the two pulses overlap spatially and temporally. The cross-correlation curve points to a 250 fs rms jitter between the two sources at the experiment. A more precise determination of the temporal fluctuation between the XUV and infrared pulses is obtained through the analysis of the single-shot sideband intensities. ©2007 American Institute of Physics

Dissociation of H2+ from a short, intense, infrared laser pulse: proton emission spectra and pulse calibration

The proton energy spectrum from photodissociation of the hydrogen molecular ion by short intense pulses of infrared light is calculated. The time-dependent Schrödinger equation is discretized and integrated. For few-cycle pulses one can resolve vibrational structure, arising from the experimental preparation of the molecular ion. We calculate the corresponding energy spectrum and analyse the dependence on the pulse time delay, pulse length and intensity of the laser for ? ~ 790 nm. We conclude that the proton spectrum is a sensitive probe of both the vibrational populations and phases, and allows us to distinguish between adiabatic and nonadiabatic dissociation. Furthermore, the sensitivity of the proton spectrum from H2+ is a practical means of calibrating the pulse. Our results are compared with recent measurements of the proton spectrum for 65 fs pulses using a Ti:Sapphire laser (? ~ 790 nm) including molecular orientation and focal-volume averaging. Integrating over the laser focal volume, for the intensity I ~ 3 × 1015 W cm-2, we find our results are in excellent agreement with these experiments.

Forensic analysis of architectural finishes using Fourier transform infrared and Raman spectroscopy, Part I: The resin bases

The ability of Raman spectroscopy and Fourier transform infrared (FT-IR) microscopy to discriminate between resins used for the manufacture of architectural finishes was examined in a study of 39 samples taken from a commercial resin library. Both Raman and FT-IR were able to discriminate between different types of resin and both split the samples into several groups (six for FT-IR, six for Raman), each of which gave similar, but not identical, spectra. In addition, three resins gave unique Raman spectra (four in FTIR). However, approximately half the library comprised samples that were sufficiently similar that they fell into a single large group, whether classified using FT-IR or Raman, although the remaining samples fell into much smaller groups. Further sub-division of the FT-IR groups was not possible because the experimental uncertainty was of similar magnitude to the within-group variation. In contrast, Raman spectroscopy was able to further discriminate between resins that fell within the same groups because the differences in the relative band intensities of the resins, although small, were larger than the experimental uncertainty.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.